KR20180127216A - Polymer resin composition, 3d printing filament including the same, and method for producing 3d printer filament - Google Patents

Abstract

The present invention relates to a polymer resin composition, a filament for three-dimensional (3D) printers including the same, and a method for producing the filament for 3D printers. To this end, the polymer resin composition comprises: a polyester copolymer A comprising a residue of a dicarboxylic acid component containing terephthalic acid and a residue of a diol component containing dianhydrohexitol; a polyester copolymer B comprising a residue of a dicarboxylic acid component including terephthalic acid and a residue of a diol component except dianhydrohexitol; and an impact reinforcement agent.

Description

TECHNICAL FIELD [0001] The present invention relates to a polymer resin composition, a filament for a 3D printer including the filament, and a method for manufacturing a filament for a 3D printer. BACKGROUND OF THE INVENTION 1. Field of the Invention [0002]

The present invention relates to a polymer resin composition, a filament for a 3D printer including the same, and a method for manufacturing a filament for a 3D printer.

3D printer is a device that manufactures products by processing and laminating materials such as liquid and powder type resin, metal powder, and solid based on design data. 3D printer technology is based on FDM (Fused Deposition Modeling), SLS Selective Laser Sintering, and SLA (Stereo Lithography Apparatus). In the FDM method, a filament-type thermoplastic material is melted in a nozzle to output in the form of a thin film. In the SLS method, a product is output by selectively irradiating a laser with a laser or an adhesive. In the SLA method, And the product is outputted by scanning.

Among the above three methods, the FDM method of using thermoplastic plastic in the form of filament is advantageous in that the production cost is lower, the printing speed is faster than other methods, and the size can be reduced. As the filament materials used in the FDM method, polylactic acid (PLA), acrylonitrile butadiene styrene (ABS), and polycarbonate (PC) are used.

However, since the FDM-type 3D printer is a method of dissolving and outputting the material by applying heat to filaments, when printing using PC and ABS as filament materials, harmful substances and odors such as bisphenol A (BPA) and styrene There is a drawback that it occurs. Specifically, PC contains bisphenol A (BPA) which is a harmful substance as a raw material. When PC is placed in a high temperature and high humidity environment, hydrolysis occurs slowly, and BPA as a constituent is separated. Separated BPA is an endocrine disruptor, and recent studies have shown that endocrine disruptors contained in synthetic resin products such as BPA not only disturb human immune function, but also increase the amount of active oxygen, the cause of cancer and aging It is reported that there is a possibility.

On the other hand, ABS uses styrene, which is a harmful substance, as a raw material. When the styrene is used as a filament material, poisonous gases and odors such as styrene are generated. It is also known that the ABS releases a large amount of carbon dioxide, which is a main cause of global warming.

 Therefore, when 3D printing is performed with the filament using the PC or ABS, harmful substances and odors such as BPA and styrene are generated. In addition, there is a problem that the shrinkage (deformation) of the molding is large during printing using the ABS, and the bed adhesion is poor and the bed temperature of 100 ° C or more is required. In the printing using the PC, high processing temperature and bed temperature are required, . Furthermore, although PLA has no harmful substances and has a low processing temperature, there is a problem that the mechanical properties and heat resistance characteristics are heated.

Therefore, filament materials used in FDM type 3D printers are required to be environmentally friendly, free from harmful substances and odors such as BPA and styrene, have excellent mechanical and thermal properties, and are capable of 3D printing at low temperatures have.

The present invention relates to a polymer resin composition which is environmentally friendly and has excellent mechanical properties and heat resistance characteristics because no harmful substances such as BPA and styrene are generated and odor is not generated, A filament for a printer, and a method for producing the filament for a 3D printer.

The present invention relates to a polyester copolymer A comprising a residue of a dicarboxylic acid component containing terephthalic acid and a residue of a diol component; A polyester copolymer B comprising a residue of a dicarboxylic acid component including terephthalic acid and a residue of a diol component; And an impact modifier, wherein the residue of the diol component of the polyester copolymer A comprises isosorbide, 1,4-cyclohexanediol, and ethylene glycol, and the moiety of the diol component of the polyester copolymer B is cyclo And a polymer resin composition comprising hexane dimethanol.

The present invention also provides a filament for a 3D printer comprising the polymer resin composition.

Further, the present invention provides a method for manufacturing a filament for a 3D printer, comprising the steps of kneading and extruding the polymer resin composition using an extruder, and winding the filament using a roller.

Hereinafter, a polymer resin composition according to a specific embodiment of the present invention, a filament for a 3D printer including the same, and a method for manufacturing a filament for a 3D printer will be described in detail.

According to one embodiment of the invention, there is provided a polyester copolymer A comprising a residue of a dicarboxylic acid component comprising terephthalic acid and a residue of a diol component; A polyester copolymer B comprising a residue of a dicarboxylic acid component including terephthalic acid and a residue of a diol component; And an impact modifier, wherein the residue of the diol component of the polyester copolymer A comprises isosorbide, 1,4-cyclohexanediol, and ethylene glycol, and the moiety of the diol component of the polyester copolymer B is cyclo A polymer resin composition containing hexane dimethanol may be provided.

The present inventors have conducted studies on a polymer resin composition having excellent mechanical properties and heat resistance characteristics without causing harmful substances and odors such as bisphenol A and styrene at the time of molding and found that the residues of dicarboxylic acid components including terephthalic acid, A polyester copolymer A comprising a residue of a diol component; A polyester copolymer B comprising a residue of a dicarboxylic acid component including terephthalic acid and a residue of a diol component; And an impact modifier, wherein the residue of the diol component of the polyester copolymer A comprises isosorbide, 1,4-cyclohexanediol, and ethylene glycol, and the moiety of the diol component of the polyester copolymer B is cyclo The polymer resin composition containing hexane dimethanol is environmentally friendly because it does not generate harmful substances and odor is not generated, and has excellent mechanical properties and heat resistance characteristics.

In the process of producing the polymer resin composition, conventional methods and apparatuses used for producing blends or mixtures of polymer resins can be used without any particular limitation. For example, a polyester copolymer A comprising a residue of a dicarboxylic acid component including terephthalic acid and a residue of the diol component; A polyester copolymer B comprising a residue of a dicarboxylic acid component including terephthalic acid and a residue of said diol component; And the impact modifier may be put in a conventional mixer, a mixer or a tumbler, and mixed through an extruder, for example, a twin-screw kneading extruder, to provide the polymer resin composition. In the course of producing the polymer resin composition, it is preferable that each of the resins is used in a sufficiently dried state.

The polymer resin composition prepared by this method can be used for electric and electronic products, mobile phone materials, interior materials such as household refrigerators and washing machines, automobile parts and interior materials, packaging materials for foods and industrial use, and particularly, It is preferable to use it as a material of a filament for an FDM type 3D printer because no harmful substances and odors are generated and the output is possible even at a low temperature.

The polymer resin composition may include 55 to 90% by weight of the polyester copolymer A, 7 to 33% by weight of the polyester copolymer B, and 0.7 to 13% by weight of the impact modifier.

The content of each component in the polymer resin composition is, for example, from 59 to 87% by weight of the polyester copolymer A, from 10 to 30% by weight of the polyester copolymer B, and from 1 to 12% by weight of the impact modifier .

As used herein, the term " residue " refers to a certain moiety or unit derived from the specific compound that is included in the result of the chemical reaction when the particular compound participates in the chemical reaction. For example, each of the 'residue' of the dicarboxylic acid component or the 'residue' of the diol component may be any of the polyester copolymers A and B formed by the esterification reaction or the polycondensation reaction, Quot; portion " means a portion derived from a part or diol component.

The 'dicarboxylic acid component' may be a dicarboxylic acid such as terephthalic acid, an alkyl ester thereof (lower alkyl ester having 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester) and / Is used to mean an acid anhydride and can react with a diol component to form a dicarboxylic acid moiety such as a terephthaloyl moiety.

By including terephthalic acid in the dicarboxylic acid component used for the synthesis of the polyester copolymers A and B, physical properties such as mechanical properties and heat resistance properties of the polyester resin composition to be produced can be improved.

The dicarboxylic acid component contained in the polyester copolymers A and B may further include an aromatic dicarboxylic acid component, an aliphatic dicarboxylic acid component, or a mixture thereof. The aromatic dicarboxylic acid component may be an aromatic dicarboxylic acid having 8 to 20 carbon atoms or 8 to 14 carbon atoms, or a mixture thereof. Examples of the aromatic dicarboxylic acid include naphthalenedicarboxylic acid such as isophthalic acid and 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, 4,4'-stilbenedicarboxylic acid, 2, 5-furandicarboxylic acid, 2,5-thiopendicarboxylic acid, and the like, but the specific examples of the aromatic dicarboxylic acid are not limited thereto.

The aliphatic dicarboxylic acid component may be an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms or 4 to 12 carbon atoms, or a mixture thereof. Examples of the aliphatic dicarboxylic acid include cyclohexanedicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid, phthalic acid, sebacic acid, succinic acid, isodecylsuccinic acid, Linear or branched alicyclic dicarboxylic acid components such as maleic acid, fumaric acid, adipic acid, glutaric acid and azelaic acid. However, the specific examples of the aliphatic dicarboxylic acid are not limited thereto.

On the other hand, the diol component used in the synthesis of the polyester copolymer A is 0.1 to 60 mol% of isosorbide, 5 to 80 mol% of 1,4-cyclohexanediol, and 5 to 80 mol% of ethylene glycol, . ≪ / RTI >

The content of the isobide may be 0.1 to 60 mol%, or 5 to 60 mol%, based on the total content of the diol component. If the content of isosorbide in the diol component is less than 0.1 mol%, heat resistance or mechanical properties of the polyester copolymer A to be produced may be insufficient. When the content of the polyester copolymer A exceeds 60 mol% There is a fear that the composition yellowing.

The diol component in the polyester copolymer A may further include at least one member selected from the group consisting of compounds represented by the following formulas (1), (2) and (3).

[Chemical Formula 1]

R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and n ₁ and n ₂ are each independently an integer of 0 to 3.

(2)

R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms.

(3)

In the above, n is an integer of 1 to 7.

The content of the polyester copolymer A in the polymer resin composition may be 55 to 90% by weight, or 59 to 87% by weight. If the content of the polyester copolymer A is less than 55% by weight, the heat resistance may be deteriorated. If the content of the polyester copolymer A is more than 90% by weight, it may be difficult to lower the extrusion processing temperature and the 3D printing nozzle temperature.

On the other hand, the polyester copolymer B contained in the polymer resin composition includes a residue of a diol component. In addition, the residue of the diol component may comprise cyclohexane dimethanol. In addition to cyclohexane dimethanol, the residue of the diol component may further include at least one member selected from the group consisting of an aromatic diol component, an aliphatic diol component, and an alicyclic diol component.

The cyclohexanedimethanol may be, for example, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol or 1,4-cyclohexanedimethanol. Particularly, the excellent heat resistance characteristics of the resin composition and For impact resistance, it may be 1,4-cyclohexanedimethanol.

The aromatic diol component may be a benzene ring and an aromatic diol having 8 to 20 carbon atoms or 8 to 14 carbon atoms, or a mixture thereof, in which two hydroxy groups are substituted on the benzene ring. Examples of the aromatic diol include biphenol, hydroquinone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, and 1,4-dihydroxynaphthalene. Specific examples of the aromatic diol include It is not.

The aliphatic diol component may be two hydroxyl group-substituted components in a compound having a chain of carbon atoms, an aliphatic diol component having 2 to 20 carbon atoms, or a mixture thereof. Examples of the aliphatic diol component include ethylene glycol, propylene glycol, butylene glycol and the like, but the specific examples of the aromatic diol are not limited thereto.

The cycloaliphatic diol component is a compound having a cyclic structure composed only of carbon and substituted with two hydroxyl groups, and the carbon bond forming the cyclic structure may be in a saturated state. For example, in addition to the cyclohexane dimethanol, the alicyclic diol component may be an alicyclic diol having 8 to 20 carbon atoms, or 8 to 14 carbon atoms, or a mixture thereof, and the like.

The polyester copolymer B contained in the polymer resin composition may be at least one selected from the group consisting of polycyclohexylenedimethylene terephthalate (PCT) and glycol-modified polycyclohexylenedimethylene terephthalate (PCTG).

Wherein the glycol-modified polycyclohexylenedimethylene terephthalate is a copolymer of a dicarboxylic acid containing terephthalic acid and a diol containing cyclohexane dimethanol, the content of cyclohexane dimethanol being 40 to 90 mol%, 45 to 85 mol% %, 50 to 80 mol%, or 50 to 75 mol%. If the content of cyclohexane dimethanol is less than 40 mol%, the crystalline region in the resin decreases and the heat resistance characteristics such as the glass transition temperature (Tg) deteriorate. When the content exceeds 90 mol%, thermal decomposition occurs due to the increase in processing temperature The transparency of the product is lowered, and the color may be unexpectedly turned yellow. In addition, the crystallization of the filament occurs during the printing process, so that the interlaminar adhesion and the transparency of the product may be deteriorated.

The glycol-modified polycyclohexylenedimethylene terephthalate may contain one or more diols other than the cyclohexane dimethanol, and examples thereof include ethylene glycol, diethylene glycol, 1,2-propanediol, 1 1,3-propanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-butanediol, 2,2- Mixture. ≪ / RTI > The amount of the diol except for the cyclohexane dimethanol is such that the sum of the total diol components relative to the dicarboxylic acid is 100 mol% in consideration of the content of cyclohexane dimethanol.

In addition, the polyester copolymer B may be an amorphous glycol-modified polycyclohexylenedimethylene terephthalate (PCTG) having a glass transition temperature of 80 ° C or higher and excellent heat resistance characteristics and not being crystallized at a low temperature after melting .

The content of the polyester copolymer B in the polymer resin composition may be 7 to 33% by weight, or 10 to 30% by weight. If the content of the polyester copolymer B is less than 7% by weight, it may be difficult to lower the processing temperature. If the content of the polyester copolymer B is more than 33% by weight, the heat resistance may be deteriorated.

The weight ratio of the polyester copolymer B to the polyester copolymer A may be 1: 0.07 to 0.55 or 1: 0.1 to 0.51. If the weight ratio is less than 1: 0.07, it may be difficult to lower the processing temperature. If the weight ratio is more than 1: 0.55, the heat resistance characteristic may be deteriorated.

The impact modifier may be a core-shell structure impact modifier, a linear structure shock modifier, or a mixture thereof.

The impact modifier of the core-shell structure may be a form in which a shell component is graft-polymerized to a core (rubber core) to form a shell. The rubber may be a diene rubber having 4 to 6 carbon atoms, an acrylic rubber, a silicone rubber, And a rubber monomer selected from the group consisting of a combination of these.

Examples of the acrylic rubber include acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, (Meth) acrylate monomers such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butylene glycol di , 4-butylene glycol di (meth) acrylate, allyl (meth) acrylate, triallyl cyanurate and the like.

The silicone rubber is prepared from cyclosiloxane. Specific examples thereof include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenyl Cyclotetrasiloxane, octaphenylcyclotetrasiloxane, and combinations thereof. ≪ Desc / Clms Page number 7 >

Unless otherwise specified herein, "(meth) acrylic acid" includes "acrylic acid" and "methacrylic acid", and "(meth) acrylate" includes "acrylate" and "methacrylate" .

Examples of the unsaturated monomer grafted on the rubber include alkyl (meth) acrylate, (meth) acrylate, acid anhydride, alkyl or phenyl nucleus-substituted maleimide, and combinations thereof. Wherein said alkyl means alkyl of 1 to 8 carbon atoms.

Specific examples of the alkyl (meth) acrylate include methyl methacrylate, ethyl methacrylate, and propyl methacrylate. Examples of the acid anhydride include carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, and the like.

For example, the impact modifier of the core-shell structure may be an alkyl methacrylate-diene rubber-aromatic vinyl graft copolymer, an alkyl methacrylate-silicone / alkyl acrylate graft copolymer, or a mixture thereof have.

On the other hand, the impact modifier having a linear structure may be a polyethylene-butyl acrylate-glycidyl methacrylate copolymer, a polyethylene-methacrylate-glycidyl methacrylate copolymer, an ethylene-alpha olefin impact modifier, A polyester elastomer impact modifier, and a polyester elastomer impact modifier.

In the polymer resin composition according to the above embodiment, the content of the impact modifier may be 0.7 to 13% by weight, or 1 to 12% by weight. If the content of the impact modifier is less than 0.7 wt%, the effect of improving the impact properties may not be exhibited. If the content of the impact modifier is more than 13 wt%, the flowability may be decreased and the processing temperature may be increased.

The polymer resin composition can be used as a material of a filament for an FDM type 3D printer, a material for an electric and electronic product and a mobile phone, an interior material for a domestic refrigerator and a washing machine, an automobile part and interior material, a food and an industrial packing material.

According to another embodiment of the present invention, a filament for a 3D printer including the polymer resin composition may be provided.

The 3D printer is operated on the principle that the filament material is melted through the nozzle and outputted on the 3D printer bed. Generally, the filament material can be output in a condition that the nozzle temperature is 270 캜 or less or 260 캜 or less, A material capable of outputting at 90 DEG C or lower or 70 DEG C or lower is preferable.

Conventionally, polycarbonate (PC), acrylonitrile butadiene styrene (ABS) and the like have been used as materials for filament for 3D printer. However, when outputting using the PC material, nozzle temperature of 300 ° C or more and bed temperature of 140 ° C or more are required , Even when an ABS material is used for output, a bed temperature of 100 DEG C or more is required, so that there is a problem that 3D printing output conditions are difficult to be widely used. Furthermore, there is a problem that bisphenol A (BPA) occurs in the PC, and harmful substances such as styrene and odor are generated. Therefore, it is required to develop a material which can output at a nozzle temperature of 270 ° C or lower and a bed temperature of 90 ° C or lower, and which does not generate harmful substances or odors.

The present inventors have conducted research on filament materials capable of 3D printing at low temperatures without causing harmful substances and odors such as bisphenol A and styrene during 3D printing and have found that the residues of dicarboxylic acid components including terephthalic acid Polyester copolymer A comprising residues of a diol component including isobarbide, 1,4-cyclohexanediol, and ethylene glycol; A polyester copolymer B comprising a residue of a dicarboxylic acid component including terephthalic acid and a residue of a diol component including cyclohexanedimethanol; And the impact modifier are environmentally friendly, have excellent mechanical properties and heat resistance characteristics, and have a nozzle temperature of 270 占 폚 or less and a temperature of not higher than 270 占 폚, 3D printing can be performed at a temperature of 90 ° C or lower.

The filaments may generally have a diameter of from 1.70 to 1.80 mm or from 2.95 to 3.05 mm. If the diameters of the filaments do not satisfy these values, the filaments are not fed to the nozzles through the gears during the operation of the 3D printer, so that printing can not be performed or the filaments are unevenly melted, The problem may be degraded.

According to another embodiment of the present invention, there is provided a method for manufacturing a filament for a 3D printer, which comprises kneading and extruding the polymer resin composition using an extruder, and winding the filament using a roller.

The polymer resin composition may be kneaded and extruded using an extruder. For example, the polymer resin composition may be extruded using a twin screw extruder (40Φ, L / D = 2) to melt extruded in a strand form. The extruder is a kind of a press molding machine, which is a reciprocating type in which a material is placed in a cylinder, a material is put in an extruding cylinder and extruded, and a continuous type in which a screw is rotated and extruded in a cylinder. The rod-like or thread-like shape of the defined monolayer can be extruded. Particularly, the screw extruder is continuously obtained a linear or tubular molded product, and can be used for extrusion-spinning of plastics and synthetic fibers (filaments).

In this embodiment, the 'kneading' means an operation of uniformly mixing by applying a mechanical shearing force. In the present invention, in order to produce a polymer optimized for 3D printing, proper mixing sequence, kneading time, and temperature Respectively.

The kneading extrusion may be extruded at a screw rotation speed of 150 to 300 rpm. If the screw rotational speed is less than 150 rpm, the thickness of the filament to be manufactured becomes thick and the filament can not be fed through the gap between the gears and can not be printed. If the screw rotational speed exceeds 300 rpm, There is a problem that the quality of the output is lowered due to uneven melting.

The extrusion of the kneading and extruding step may be performed at 240 to 320 ° C, or 260 to 300 ° C. If the temperature is less than 240 ° C during extrusion, it is difficult to blend the polymer because the polymer can not be melted. If the temperature is more than 320 ° C, denaturation of the polymer may occur.

After the kneading and extruding step, the step of cooling the kneaded extruded polymer resin composition in a water bath may further include a step of cooling the extruded polymer resin composition. In addition, the polymer resin composition that has been cooled in the water bath may be wound using a roller to produce filaments.

When the polymer resin composition is wound using a roller, a filament having a certain thickness can be produced. At this time, the speed of the motor for rotating the roller during the winding may be 10 to 500 m / min. If the speed of the motor is less than 10 m / min, the diameter of the filament becomes thicker than the basic diameter and productivity may be lowered. If the speed is more than 500 m / min, the diameter of the filament becomes thinner than the basic diameter, There may be a problem that the property is not good.

The filament may have a diameter of 1.70 to 1.80 mm or 2.95 to 3.05 mm. If the diameters of the filaments do not satisfy these values, the filaments are not fed to the nozzles through the gears during the operation of the 3D printer, so that printing is impossible or the filaments are melted insufficiently, May be deteriorated.

According to the present invention, there is provided a polymeric resin composition which is environment-friendly and has excellent mechanical properties and heat resistance characteristics because no harmful substances such as BPA and styrene are generated and odor is not generated, A filament for an excellent 3D printer, and a method for manufacturing a filament for the 3D printer.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[ Example  1 to 7: Preparation of Polymeric Resin Composition]

Terephthalic acid-isosorbide-1,4-cyclohexanediol-ethylene glycol copolymer (ECOZEN, a high-impact eco-friendly resin manufactured by SK Chemicals Co., Ltd.)) was added to a twin screw extruder (Φ: 40 mm, L / A glycol-modified polycyclohexylenedimethylene terephthalate resin (PCTG, manufactured by SK Chemicals Co., Ltd.), and a polyethylene-butyl acrylate-glycidyl methacrylate copolymer (impact modifier of Dupont Co.), which is a linear structure impact modifier, As other additives, acrylonitrile-styrene-glycidyl methacrylate copolymer (SAG-005 of SUNNY FC, China), phenolic primary oxidation stabilizer (AO-60 of ADEKA, Japan), and phosphorus secondary oxidation stabilizer I-168 from BASF) was added. Each component was uniformly kneaded and extruded by the contents of the following Table 1 to prepare pellets.

[ Comparative Example  1 to 6: Preparation of Polymeric Resin Composition]

The components were added to the biaxial kneading extruder (Φ: 40 mm, L / D = 40) in the composition shown in Table 1, and then uniformly kneaded and extruded to prepare pellets.

(unit:
weight%) Example Comparative Example  One  2  3  4  5  6 7 One 2 3 4 5 6 Ecozen 86 66 87 79 67 59 87 91 61 78 74 96 PC 66 PCTG 10 30 10 10 30 30 5 35 20 20 PCT 10 30 Impact modifier 3 3 One 10 One 10 3 3 3 0.5 15 3 3 SAG-005 One One One One One One One One One One One One One AO-60 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 I-168 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15

[ Experimental Example : Measurement of Physical Properties of Test Piece and Filament Prepared from Polymeric Resin Composition]

The pellets produced according to Examples 1 to 7 and Comparative Examples 1 to 6 were injected at the same temperature at 240 ° C. by means of an injection machine and then the injected specimens were measured by the methods of Experimental Examples 1 to 3 And the measurement results are shown in Table 2 below. Filaments prepared using an extruder (Twin screw extruder, 40Φ, L / D = 2) were tested for printing characteristics by the method of Experimental Example 4, and the measurement results are shown in Table 2 below.

Experimental Example  1: Heat resistance measurement

According to ASTM D648, test specimens were prepared and heat resistance was measured using a heat deflection temperature tester (HDT Tester, Toyoseiki).

Experimental Example  2: Measurement of tensile properties

Tensile strength and elongation were measured using a universal testing machine (Zwick Roell Z010) by making test specimens according to ASTM D638.

Experimental Example  3: Impact strength measurement

(Thickness of specimen: 1/8 " and 1/4 ") according to ASTM D 256 and the impact strength value was measured using an Impact Tester (Yasuda). The measurement conditions were measured with an Izod notched type at a temperature of 25 캜.

Experimental Example 4: 3D  Measuring printing characteristics

Using a 3D printer (Lulzbot TAZ6), 100 x 100 x 4 mm flat plate specimens were printed. At this time, the nozzle temperature (or the processing temperature) and the bed temperature were confirmed.

unit Example Comparative Example One 2 3 4 5 6 7 One 2 3 4 5 6 Heat resistance
(HDT) ℃ 104 98 103 104 98 97 107 105 89 101 102 108 120 The tensile strength Kg / cm ² 536 516 535 524 500 490 512 540 480 510 420 590 580 Elongation % 178 226 170 250 180 250 228 190 260 186 280 183 205 Impact strength
(1/8 ") J / m 856 856 320 856 345 856 850 856 856 130 856 856 856 Impact strength
(1/4 ") J / m 428 428 230 428 253 428 428 428 428 90 428 428 428 Nozzle temperature ℃ 250 240 250 250 240 240 250 270 240 250 260 270 280 Bed temperature ℃ 70 ~ 80 70 ~ 80 70 ~ 80 70 ~ 80 70 ~ 80 70 ~ 80 70 ~ 80 70 ~ 80 70 ~ 80 70 ~ 80 70 ~ 80 70 ~ 80 70 ~ 80

As can be seen from the above measurement results, it was found that the examples were superior in heat resistance, impact resistance, tensile properties, and 3D printing characteristics to the comparative examples. Specifically, in Comparative Examples 1, 5 and 6, the nozzle temperature was significantly higher than that in Examples, Comparative Example 2 had significantly lower heat resistance than Examples, Comparative Example 3 had significantly lower impact strength than Examples, It was confirmed that the tensile strength of Comparative Example 4 was significantly lower than that of the Examples.

Claims (16)

A residue of a dicarboxylic acid component including terephthalic acid; Polyester copolymers A comprising residues of a diol component including isosorbide, 1,4-cyclohexanediol, and ethylene glycol;
A residue of a dicarboxylic acid component including terephthalic acid; A polyester copolymer B comprising residues of a diol component including cyclohexanedimethanol; And
A polymeric resin composition comprising an impact modifier.
The polyester copolymer A as claimed in claim 1, wherein the polyester copolymer A comprises from 0.1 to 60 mol% of isosorbide, from 5 to 80 mol% of 1,4-cyclohexanediol, and from 5 to 80 mol% of ethylene glycol .
The method according to claim 1, wherein the polymer resin composition is a filament for a 3D printer Polymer resin composition.
The polymer resin composition according to claim 1, wherein the polymer resin composition comprises a polymer resin composition comprising 55 to 90 wt% of the polyester copolymer A, 7 to 33 wt% of the polyester copolymer B, and 0.7 to 13 wt% of the impact modifier .
The polymeric resin composition according to claim 1, wherein the polymeric resin composition comprises 59 to 87% by weight of the polyester copolymer A, 10 to 30% by weight of the polyester copolymer B, and 1 to 12% by weight of the impact modifier .
The polymer resin composition according to claim 1, wherein the weight ratio of the polyester copolymer B to the polyester copolymer A is 1: 0.07 to 0.55.
The polymer resin composition according to claim 1, wherein the polyester copolymer B is polycyclohexylenedimethylene terephthalate (PCT), glycol-modified polycyclohexylenedimethylene terephthalate resin (PCTG), or a mixture thereof.
The polymeric resin composition according to claim 1, wherein the impact modifier is a core-shell structure impact modifier, a linear structure impact modifier, or a mixture thereof.
The impact modifier of claim 8, wherein the impact modifier of the core-shell structure is an alkyl methacrylate-diene rubber-aromatic vinyl graft copolymer, an alkyl methacrylate-silicone / alkyl acrylate graft copolymer, By weight.
The impact modifier according to claim 8, wherein the impact modifier of the linear structure is selected from the group consisting of a polyethylene-butyl acrylate-glycidyl methacrylate copolymer, a polyethylene-methacrylate-glycidyl methacrylate copolymer, an ethylene- , A silicone-based impact modifier, and a polyester elastomer impact modifier.
A filament for a 3D printer, comprising the polymer resin composition according to any one of claims 1 to 10.
10. A method for producing a polymeric resin composition, comprising the steps of: kneading and extruding the polymeric resin composition of any one of claims 1 to 10 using an extruder; And
A method for producing a filament for a 3D printer, comprising the step of winding a polymer resin composition by extrusion using a roller to produce a filament.
13. The method according to claim 12, wherein the kneading extrusion has a screw rotating speed of 150 to 300 rpm.
The method of claim 12, wherein the kneading extrusion is performed at a temperature of 240 to 320 ° C.
13. The method according to claim 12, wherein the roller is rotated by a motor, and the speed of the motor is 10 to 500 m / min.
The method of manufacturing a filament according to claim 12, further comprising, after the kneading and extruding step, cooling the kneaded extruded polymer resin composition in a water bath.